CN101367524B - Improved trichlorosilane synthesis method and apparatus - Google Patents
Improved trichlorosilane synthesis method and apparatus Download PDFInfo
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- CN101367524B CN101367524B CN2008101990605A CN200810199060A CN101367524B CN 101367524 B CN101367524 B CN 101367524B CN 2008101990605 A CN2008101990605 A CN 2008101990605A CN 200810199060 A CN200810199060 A CN 200810199060A CN 101367524 B CN101367524 B CN 101367524B
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- hydrogen chloride
- chloride gas
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Abstract
The invention discloses a method for synthesizing the improved trichlorosilane, which comprises the steps: further drying the hydrogen chloride gas, in which, after the hydrogen chloride gas is dried by a three-level cooler, the hydrogen chloride gas is dried by a further drying tower that adopts the chlorsilane solution as the deicer, and finally the hydrogen chloride gas that is dried enters into a synthesis reactor to be reacted with the silicon powder to synthesize the trichlorosilane. The invention not only can improve the productivity of the trichlorosilane and can reduce the consumption of the silicon powder, but also can realize the cycling application of the resource. Moreover, the invention can reduce the corrosion rate of the device and the blocking rate of the pipeline.
Description
Technical field
The present invention relates to a kind of trichlorosilane synthesis method and device.
Background technology
Trichlorosilane is the important intermediate of synthesizing organo-silicon, also is the main raw material of preparation polysilicon.In recent years, along with the develop rapidly of the rate of growth and the polysilicon industry of China's organosilicon industry average annual 20%, the demand of trichlorosilane is sharply increased.Hydrogen chloride gas is the indispensable raw material of synthesizing trichlorosilane, because the hydrogen chloride gas that synthesis method is produced contains higher moisture content usually, not only cause the heavy corrosion and the line clogging of equipment, and moisture content is very harmful to synthesizing trichlorosilane, because the Si-O key is more more stable than Si-Cl key, hydrolysis more easily takes place in the reaction product trichlorosilane, and the productive rate of trichlorosilane is reduced.The hydrogenchloride water content is bigger, then trichlorosilane content is lower in the product, when the hydrogenchloride water content is 1000ppm, then the trichlorosilane productive rate is lower than 80%, and moisture content can also form the oxide film of one deck densification at silicon powder surface, cause the silica flour passivation, the silica flour unit consumption increases in the building-up process thereby make, and then increases production cost.
Domestic general employing cold method or vitriol oil method dry hydrogen chloride gas adopt these two kinds of method exsiccant hydrogen chloride gas body water contents to be reduced at present, but still are higher than 500ppm, can't reach the effect of depth drying.It is synthetic to adopt these two kinds of method exsiccant hydrogen chloride gas to be used for trichlorosilane, and the productive rate of trichlorosilane is improved, but still is lower than 87%.Handle if can carry out depth drying,, then can reduce the unit consumption of silica flour and the productive rate of raising trichlorosilane, and then reduce the production cost of trichlorosilane to reduce the water content of hydrogen chloride gas as far as possible to hydrogen chloride gas.
In traditional trichlorosilane synthesis technique, generally be that hydrogen chloride gas is through one, two, three dry trichlorosilane synthetic furnace that directly enters afterwards, the trichlorosilane that synthesizes reclaims product through after the rectifying, still liquid after the rectifying is then handled as by product, shortcoming is that product yield is low, and by product is not recycled.Though become the method for trichlorosilane to improve the yield of trichlorosilane by the silicon tetrachloride in the by product being carried out hydrogenating reduction theoretically, yet this method is to be difficult to find the ideal catalyzer, the energy consumption and the cost that make the hydrogenation of silicon tetrachloride reduction reclaim trichlorosilane heighten, and are difficult to use in suitability for industrialized production.
Summary of the invention
Purpose of the present invention just provides a kind of unit consumption that both can reduce silica flour, improves the productive rate of trichlorosilane, can realize the synthetic method of the modified version trichlorosilane that resource circulation is utilized again.
The present invention is achieved through the following technical solutions:
A kind of modified version trichlorosilane synthesis method, this method comprises a step of hydrogen chloride gas being carried out depth drying, hydrogen chloride gas is through after three grades of water cooler dryings, by with chlorosilane solution being the depth drying tower drying of water-removal agent, the hydrogen chloride gas after super-dry enters in the synthesis reaction vessel and reacts synthesizing trichlorosilane with silica flour then again.
Through the hydrogen chloride gas (500ppm water content) behind the three-stage drying again through being the depth drying tower drying of water-removal agent with chlorosilane solution, chlorosilane be hydrolytic activity than higher material, as silicon tetrachloride, wait and meet behind the water very easily that hydrolysis generates hydrogen chloride gas.The hydrogen chloride gas that contains moisture then can remove the moisture in the de-chlorine hydride by chlorosilane solution, and the water content in the hydrogenchloride will drop to less than 100ppm.Simultaneously can also generate hydrogenchloride, thereby can improve the productive rate of trichlorosilane, reduce the unit consumption of silica flour.Can also reduction equipment be corroded, the probability of line clogging.
Further improvement of the present invention is:
Water-removal agent chlorosilane solution is selected silicon tetrachloride solution.From the trichlorosilane building-up reactions:
Silicon tetrachloride is a by product in the trichlorosilane building-up reactions as can be known, and silicon tetrachloride solution not only can be removed the moisture in the de-chlorine hydride, SiCl
4+ H
2O → SiO
2+ HCl, and small part can also play the generation that suppresses the synthetic side reaction of trichlorosilane with the silicon tetrachloride that hydrogen chloride gas enters into the trichlorosilane Reaktionsofen.Thereby further improve the productive rate of trichlorosilane.
Particularly can select the still liquid after the rectification and purification in the production process of trichlorosilane for use.Because in the trichlorosilane building-up process, its by product is a silicon tetrachloride, if be used for the drying of hydrogenchloride raw material with these by products, both can remove the moisture in the de-chlorine hydride, silicon tetrachloride in the still liquid enters trichlorosilane synthetic furnace simultaneously, can suppress the generation of side reaction, thereby reach the purpose of the production efficiency that improves trichlorosilane.Yet can realize the resource circulation utilization, promptly the still liquid after the rectifying be recycled, can improve the yield of trichlorosilane product.
Perhaps water-removal agent is selected the by product in the polysilicon production process for use, because in Siemens Method synthesised polycrystalline silicon technology, be to adopt highly purified trichlorosilane to be reduced into silicon, its by product is a large amount of silicon tetrachloride, these silicon tetrachloride as by-product purity are than higher, also can be used for dry hydrogen chloride gas, realize the resource circulation utilization.
Another object of the present invention provides a kind of synthesizer of modified version trichlorosilane.
A kind of modified version trichlorosilane synthesizer, this device is provided with the depth drying tower that is used for hydrogen chloride gas is carried out depth drying between the synthetic furnace of three grades of water coolers of hydrogenchloride and trichlorosilane.
Wherein the water-removal agent of drying tower is preferentially selected the still liquid after the rectification and purification in the production process of trichlorosilane for use.At this moment the depth drying tower is communicated with rectifying tower in the production process of trichlorosilane, hydrogen chloride gas enters from the bottom of depth drying tower, still liquid after the rectification and purification enters from the top of depth drying tower, hydrogen chloride gas is washed drying, and the hydrogen chloride gas behind depth drying comes out to enter synthesis reaction vessel from cat head.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
The synthetic method schema of trichlorosilane among Fig. 1 embodiment 1,2,3.
Fig. 2 is the synthetic method schema of trichlorosilane among the embodiment 4,5,6.
Embodiment
Embodiment 1
Hydrogen chloride gas is through after the three-stage drying, enter in the tower from the bottom of depth drying tower, residual still liquid sprays from the top of depth drying tower and enters in the tower after the trichlorosilane rectifying with silicon tetrachloride content 99%, hydrogen chloride gas is washed drying, and the hydrogen chloride gas behind depth drying comes out to enter in the synthesis reaction vessel from cat head and reacts synthesizing trichlorosilane with silica flour.The results are shown in Table 1.
Embodiment 2
Hydrogen chloride gas is through after the three-stage drying, and residual still liquid carries out depth drying after the trichlorosilane rectifying with silicon tetrachloride content 80% again, enters trichlorosilane synthetic furnace then and carries out building-up reactions, the results are shown in Table 1.
Embodiment 3
Method is with embodiment 1, and hydrogen chloride gas is through after the three-stage drying, and residual still liquid carries out depth drying after the trichlorosilane rectifying with silicon tetrachloride content 15% again, enters trichlorosilane synthetic furnace then and carries out building-up reactions, the results are shown in Table 1.
Embodiment 4
Method is with embodiment 1, and hydrogen chloride gas uses the by product (silicon tetrachloride content 96%) of polysilicon to carry out depth drying through after the three-stage drying again, enters trichlorosilane synthetic furnace then and carries out building-up reactions, the results are shown in Table 1.
Embodiment 5
Method is with embodiment 1, and hydrogen chloride gas is through after the three-stage drying, carries out depth drying with 99.9% analytical pure silicon tetrachloride reagent again, enters trichlorosilane synthetic furnace then and carries out building-up reactions, the results are shown in Table 1.
Embodiment 6,
Hydrogen chloride gas is used 90% the capable depth drying of dichloro-dihydro silicon again through after the three-stage drying, enters trichlorosilane synthetic furnace then and carries out building-up reactions, the results are shown in Table 1.
Comparative Examples
According to a conventional method, hydrogen chloride gas reacts through directly entering trichlorosilane synthetic furnace behind the three-stage drying earlier, and gained the results are shown in Table 1.
Table 1
| Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Hydrogenchloride water content/ppm | 600 | 60 | 76 | 100 | 71 | 58 | 75 |
| Silica flour consumption kg/t trichlorosilane | 260 | 220 | 228 | 235 | 231 | 238 | 233 |
| Trichlorosilane productive rate/% | 85 | 96.3 | 95.0 | 93.2 | 95.2 | 97.1 | 94.8 |
Claims (7)
1. modified version trichlorosilane synthesis method, it is characterized in that: this method comprises a step of hydrogen chloride gas being carried out depth drying, hydrogen chloride gas is at first through three grades of water cooler dryings, make the water content of hydrogen chloride gas drop to 500ppm, again by with the silicon tetrachloride solution being the depth drying tower drying of water-removal agent, the water content of hydrogenchloride is reduced to below the 100ppm, enter in the synthesis reaction vessel through the hydrogen chloride gas behind the depth drying and react synthesizing trichlorosilane with silica flour.
2. a kind of modified version trichlorosilane synthesis method according to claim 1 is characterized in that: the silicon tetrachloride content of described silicon tetrachloride solution is 15%-100%.
3. a kind of modified version trichlorosilane synthesis method according to claim 1 is characterized in that: described silicon tetrachloride solution is the still liquid after the trichlorosilane rectification and purification in the production process of trichlorosilane.
4. a kind of modified version trichlorosilane synthesis method according to claim 3 is characterized in that: the silicon tetrachloride content of the still liquid after the described trichlorosilane rectification and purification is more than 80%.
5. a kind of modified version trichlorosilane synthesis method according to claim 1 is characterized in that: described silicon tetrachloride solution is the by product in the polysilicon production process.
6. modified version trichlorosilane synthesizer, it is characterized in that: this device is provided with the depth drying tower that is used for hydrogen chloride gas is carried out depth drying between the synthetic furnace of three grades of water coolers of hydrogenchloride and trichlorosilane, and it is that water-removal agent carries out drying to hydrogen chloride gas that the depth drying tower adopts silicon tetrachloride solution.
7. a kind of modified version trichlorosilane synthesizer according to claim 6, it is characterized in that: the depth drying tower is communicated with rectifying tower in the production process of trichlorosilane, hydrogen chloride gas enters from the bottom of depth drying tower, still liquid after the rectification and purification enters from the top of depth drying tower, hydrogen chloride gas is washed drying, and the hydrogen chloride gas behind depth drying comes out to enter synthesis reaction vessel from cat head.
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| CN106006648A (en) * | 2016-05-17 | 2016-10-12 | 山东瑞川硅业有限公司 | Method for preparing trichlorosilane |
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